气雾化低钴贮氢AB5型合金的电化学性能和Rietveld分析

用快速凝固气体雾化法制备了低钴系列贮氢合金MlMi4.3-xCoxMn0.4Al0.3(x=0.75,0.45,0.29,0.1,Ml为宜镧混合稀土）并测试其电化学性能。气雾化法可显著提高贮氢合金电极的充－放电循环稳定性,x=0.45时合金的循环寿命与商用铸态合金的寿命相当。最大放电容量随着Co含量的增加,先增大后减小,在x=0.29时出现极大值（304．4mAh/g）。结合循环寿命和最大放电容量两个性能指标,x=0.45时的合金具有良好的综合电化学性能。采用Rietveld法（多晶衍射图形拟合法）对其精细结构进行分析,合金仍保持母合金LaNi5的CaCu5型六方晶系结构,合金的晶胞体积对其循环寿命和最大放电容量起决定作用。     

Al元素对ML(NiCoMnAlFe)_(5.5)贮氢合金微结构和电化学性能的影响

用熔体快淬法制备了稀土系AB_5型ML(NiCoMnFe)_(5.5-x)Al_x(x=0.1～0.3)贮氢合金,在氩气气氛中1000℃下对样品进行热处理,通过X射线衍射、PCT和电性能测试等分析了铝元素对AB5型贮氢合金微观组织和电化学性能的影响。结果显示,热处理样品组织主要由CaCu_5型相组成,组织结构中含有少量NiFe杂相,Al=0.30时合金晶胞体积最大88.49?。PCT测试表明,当Al元素部分替代Ni后,合金的吸氢平台压力减小、吸放氢平台变得比较平坦,x=0.10时合金最大吸氢量为0.9146H/M。电化学性能分析,ML(NiCoMnFe)_(5.5-x)Al_x(x=0.1～0.3)合金具有较好的活化性能,x=0.20合金具有较好的综合性能,最高放电容量337.2mAh/g、循环寿命329次。     

不同化学计量比稀土镁基贮氢电极合金结构和电化学性能

用冷坩锅磁悬浮熔炼的方法制备了不同化学计量比的La0.7Mg0.3(Ni0.85Co0.15)x(x=3.0,3.1,3.2,3.3,3.4,3.5)稀土镁基贮氢电极合金,采用X射线衍射和三电极测试体系研究了合金的相结构和电化学性能。X射线衍射分析结果表明,该系列合金均由(La,Mg)Ni3相、(La,Mg)2Ni7相、LaNi5相及少量杂质相组成,为多相结构;随着化学计量比x的增加,(La,Mg)Ni3相的含量降低,相应LaNi5相的含量增加。电化学测试结果表明,该系列合金的最大放电容量均高于目前已商品化的稀土基AB5型贮氢电极合金的最大放电容量(310~330 mAh.g-1),且当x=3.4时,合金的最大放电容量可达395.4 mAh.g-1,较AB5型合金高约30%,是合金中各相的含量比例较为合适的结果;该系列合金活化性能、倍率放电性能良好,并随着化学计量比x的增加得到进一步改善,这与同时作为贮氢相和催化相的LaNi5相含量的增加有关;在电化学吸放氢循环过程中,合金的循环稳定性较差,有待进一步提高。     

化学计量比对AB5型贮氢合金相结构及电化学性能的影响

对低钴稀土系贮氢合金Ml(Ni0.78Co0.08Al0.06Mn0.08)x(4.8≤x≤5.4)的相结构及电化学性能进行了研究.结果表明在4.8≤x≤5.2的合金中除CaCu5型结构的主相之外,还出现LaNi3第二相,而且合金中第二相(LaNi3)的析出量随着x值的增大而减少,化学计量比x=5.4的合金则有富镍相析出,B侧合金化使低钴贮氢合金形成单相AB5型合金的化学计量比由x=5.0增大至5.2～5.4之间.四种不同化学计量比合金的活化性能都较好,合金的最大放电容量随化学计量比x的增大而增加,过化学计量比(x=5.4)合金具有最大的放电容量,最优的放电电压特性及最佳的循环稳定性,且其高倍率放电性能也较好.     

化学计量比对稀土-镁基合金结构和性能的影响

文章研究不同化学计或比的稀土-镁基贮氢合金Mn0.9Mg0.1(NiCoMnAl)5x(x=0.75,0.80,0.85,0.90)相的结构和电化学性能.研究表明,Mn0.9Mg0.1(NiCoMnAl)5x合金的主相均由LaNi5相和LaNi3相组成.但当x≤0.80时,合金中还有LaNi2.28相析出.合金电极的最大放电容量和高倍率性能都随着x值的增大先增加后减少,当x=0.80时,都达到最大值;合金电极在243 K时的放电容量随着x值的增加有显著提高;合金电极的循环稳定性随着x值增大而提高.     

Co替代Ni对A2B7型贮氢电极合金相结构及电化学性能的影响

采用感应熔炼方法制备了La0.75Mg0.25Ni3.5-xCox(x=0,0.25,0.75,1)四元贮氢合金,系统地研究了合金B侧Co对Ni部分替代对合金相结构及电化学性能的影响.X衍射(XRD)分析表明,La0.75Mg0.25Ni3.5-xCox由(La,Mg)2Ni-7相(包括Gd2 Co7型高温相和Ce2 Ni7型低温相)组成.此外,随着Co元素的加入,该类合金中出现CaCu5型LaNi5相.电化学测试表明,随Co含量的增加,合金电极活化次数增大,合金电极的最大放电容量增大,合金的最大放电容量由x =0.25时的376.53 mAh/g增加到x=1时的401.62mAh/g,氢扩散系数增大,循环稳定性变差,合金的高倍率放电性能降低,Co含量对合金电极高倍率放电性能HRD值的影响与对合金电极交换电流密度的影响趋势一致,这表明电极合金表面的电化学反应对合金的动力学性能影响更大.     

A2B7型La0.75Mg0.25Ni3.5-xFex(x=0～0.3)贮氢合金相结构及电化学性能研究

采用感应熔炼方法制备了La0.75Mg0.25Ni3.5-xFex(x=0.0.05,0.1,0.2,0.3)四元贮氢合金,系统地研究了合金B侧Fe对Ni部分替代对合金相结构及电化学性能的影响.X射线衍射(XRD)分析表明,La0.75Mg0.25Ni3.5-xFex由(La,Mg)2Ni7相(包括Gd2Co7型高温相和Ce2Ni7型低温相)组成.此外,随着Fe元素的加入,该类合金中出现CaCu5型LaNi5相,且随着Fe含量的增加而增多.电化学测试表明,随Fe含量的增加,合金电极活化次数变化不大,而其最大放电容量呈现先增后减的趋势,合金的最大放电容量由x=0.05时的376.21 mAh·g -1下降到x=0.3时的340.89 mAh·g-1;合金的高倍率放电性能随着Fe含量的增加而降低,当电流密度为900 mA·g-1时,合金的高倍率放电性能由83.66%(x=0)减小到62.23%(x=0.3);循环稳定性先增加后下降.     

粉末冶金法制备La_(0.75)Mg_(0.25)Ni_(3.5-x)Mn_x(x=0-0.4)合金及其电化学贮氢性能研究

为了改善稀土系A_2B_7型贮氢合金的电化学贮氢性能,采用粉末冶金方法制备的La_(0.75)Mg_(0.25)Ni_(3.5-x)Mn_x(x=0,0.1,0.2,0.3,0.4)贮氢合金,研究少量Mn替代Ni对合金相结构和电化学性能的影响。结果表明:合金由La Ni5、La2Ni7两相组成,随着Mn含量的增加,两相晶胞逐渐膨胀。Mn的加入能显著改善合金的电化学性能,然而过高的Mn含量会对合金的放电性能带来不利影响。其中La_(0.75)Mg_(0.25)Ni_(3.2)Mn_(0.3)合金电极的最大放电容量为362.3m Ah/g,经过100次循环后容量保持率为69.5%。此外,合金电极的高倍率放电性能、线性极化曲线以及电化学交流阻抗谱的测试均表明合金的电化学动力学性能随着Mn含量的增加先增大而后减小。     

镁含量对稀土-镁-镍系A2B7型储氢合金电极自放电性能的影响

系统研究了Mg元素对退火态A2B7型储氢合金La0.7-xY0.1Gd0.2MgxNi3.35Al0.15(x=0～0.4)电极自放电性能的影响。结果表明,退火态合金主要由Ce2Ni7(或Gd2Co7)型、Pr5Co19型、CaCu5型和PuNi3型相组成,Mg含量对合金组成和相结构有重要的影响,低镁含量有利于提高合金组织中Ce2Ni7型相的丰度,高镁含量易出现大量的CaCu5型和PuNi3型相。电化学测试表明,循环稳定性及电化学放电容量随Mg含量的增加而呈现先降低后升高的趋势,x=0.15,0.17合金电极具有最高的循环稳定性(S100=90%)和最大的电化学放电容量(368mAh.g-1)。Mg含量对合金电极的荷电保持率和开路电位影响显著,搁置7 d后的电极荷电保持率从7.9%(x=0)增加到59.7%(x=0.17),然后又降低到1.8%(x=0.4),表明适量的Mg含量可以改善合金的自放电性能,其中合金电极自放电时的可逆容量损失占97.5%以上,不可逆损失仅占0.4%～2.5%。合金电极的荷电保持率随合金PCT曲线放氢平台压力的升高而减小,其中氢致非晶态(x=0)和具有较高放氢平台压力的多相组织合金电极(x=0.4)的自放电率较大,荷电保持率最小。合金的腐蚀电流Icorr与电极的不可逆容量损失存在一定对应关系,当x=0.15～0.17时,合金的耐腐电流较小,其自放电时的不可逆容量损失最低,循环寿命也较佳。     

Co含量对La0.55Pr0.05Nd0.15Mg0.25Ni3.5-xCoxAl0.25（x=0～0.4）储氢合金电极性能的影响

采用电磁感应悬浮炉制备La0.55Pr0.05Nd0.15Mg0.25Ni3.5-xCoxAl0.25(x=0,0.1,0.2,0.3,0.4)系列合金,研究Co含量对合金的相结构、吸放氢性能和电化学性能的影响。研究结果表明,该系列合金主要由LaNi5、Nd2Ni7相组成。当Co含量大于0.2时,合金中出现La2Ni7相。压强-吸氢量-温度(Pressure-Content-Temprature)测试显示在303 K温度下,合金具有良好的吸氢性能,当x=0.4时合金的最大吸氢量为1.29(质量分数,%)。电化学测试表明:随x值变化,合金电极的最大放电容量分别为340.0(x=0.0)、346.6(x=0.1)、370.0(x=0.2)、320.0(x=0.3)和346.6(mA.h)/g(x=0.4);随Co含量增加,合金电极容量保持率不断增加,高倍率放电性能先增加后减小,循环伏安曲线、氢在合金体中的扩散系数D共同反映了合金电极的动力学特性。     

镍氢电池用贮氢合金多元化降钴的研究

 为了降低贮氢合金中的钴含量，从而降低镍氢电池的价格，在贮氢合金MlNi355Co075Mn04Al03的基础上，依次添加铜、铬、锌及铁元素，得到稀土基多元贮氢合金，并测试和分析了它们的放电容量、循环稳定性以及微观结构。结果表明，采用适量的铜、铬、锌及铁替代钴所得到的低钴贮氢合金仍具有较高的放电容量和较好的循环稳定性，而且其相结构并未改变。     

Effects of Strip Casting and Annealing on Electrochemical Properties of LPCNi3.55Co0.75Mn0.4Al0.3 Hydrogen Storage Alloys

The effect of thickness (1～10 mm) of the ingots on the electrochemical properties of as-cast and annealed strip cast LPCNi3.55Co0.75Mn0.4Al0.3 hydrogen storage alloys was investigated. It is found that the 0.2 C discharge capacity of as-cast LPCNi3.55Co0.75Mn0.4Al0.3 alloy increases with the increase of the thickness of the ingots. As-cast alloy with the thickness of 10 nun shows better activation property, higher 1C discharge capacity and better cyclic stability than others.It is mainly contributed to its larger unit cell volume and less internal stress. Annealed LPCNi3.55Co0.75Mn0.4Al0.3 alloywith the thickness of 3 mm shows much better comprehensive electrochemical properties than as-cast one; The cyclic stability of the alloy with the thickness of 6 mm and the activation properties of the alloys with the thickness of 3～6 mm are improved after annealing. It is mainly owing to the great release of intemal stress and the decrease fo the segregation of Mn in the alloys.     

Phase Structure and Electrochemical Properties of Rare Earth Based Hydrogen Storage Alloys

The rare earth based hydrogen storage alloys MmxM1 1 - x ( Ni3.55 Co0.75 Mn0.4 A10.3 ) ( x = 0 ～ 0.5 ) were investigated in this work.Adjusted Ml: Mm ratio to change the content of La,Ce,Pr and Nd in the alloys and then to change the phase structure, the influences of phase structure on the electrochemical properties were analyzed.The results indicate that the main phase of all alloys is LaNi5 with CaCu5 type structure and the crystal lattices constants of LaNi5 are changed with increasing x value, i.e, decreased a-axis, increased c-axis and axis ratio and nonlinear decreased crystal volume.The crystal volume of the alloy with x = 0.3 is larger than others.There is second phase A1LaNi4 in alloys when x≥0.3, which decrease the discharge capacity, but increase the cycling stability and high rate discharge ability.Compared comprehensively, the alloy with x = 0.3 shows the higher discharge capacity and the better cycling stability.     

多元化降钴对贮氢合金性能的影响

为了降低贮氢合金中的钴含量，从而降低镍氢电池的价格，在贮氢合金M1Ni3．55Co0．75Al0．3Mn0．4的基础上，依次添加Cu、Cr、Zn、Fe元素，得到稀土基多元贮氢合金，并对其放电容量和循环稳定性进行了测试和分析。结果表明，适量的Cu、Cr、Zn、Fe替代Co，仍能使贮氢合金具有较高的放电容量和较好的循环稳定性。     

Structure and electrochemical hydrogen storage characteristics of the as-cast and annealed La0.8-xSmxMg0.2Ni3.15Co0.2Al0.1Si0.05 （x=0-0.4） alloys

In order to ameliorate the electrochemical cycle stability of the RE-Mg-Ni based A2B7-type electrode alloys, the Mg content in the alloy was reduced and La in the alloy was partially substituted by Sm. The La0.8-xSmxMg0.2Ni3.15Co0.2Al0.1Si0.05 (x=0, 0.1, 0.2, 0.3, 0.4) elec-trode alloys were fabricated by casting and annealing. The microstructures of the as-cast and annealed alloys were characterized by XRD and SEM. The electrochemical hydrogen storage characteristics of the as-cast and annealed alloys were measured. The results revealed that all of the experimental alloys mainly consisted of two phases: (La,Mg)2Ni7 phase with the hexagonal Ce2Ni7-type structure and LaNi5 phase with the hexagonal CaCu5-type structure. As Sm content grew from 0 to 0.4, the discharge capacity and the high rate discharge ability (HRD) first in-creased and then decreased for the as-cast and annealed alloys, whereas the capacity retaining rate (S100) after 100 cycles increased continuously.     

A study on hydrogen storage and electrochemical properties of La_（0.55）Pr_（0.05）Nd_（0.15）Mg_（0.25）Ni_（3.5） （Co_（0.5）Al_（0.5））_x （x=0.0, 0.1, 0.3, 0.5） alloys

The La0.55Pr0.05Nd0.15Mg0.25Ni3.5(Co0.5Al0.5)x(x=0.0, 0.1, 0.3, 0.5) alloys were prepared by magnetic levitation melting under an Ar atmosphere, and the effects of Co and Al on the hydrogen storage and electrochemical properties were systematically investigated by pressure composition isotherms, cyclic voltammetry, Tafel polarization and electrochemical impedance spectroscopy testing. The results showed that the alloy phases were mainly consisted of (La,Pr)(Ni,Co)5, LaMg2Ni9, (La,Nd)2Ni7 and LaNi3 phases, and the cell volumes of (La,Pr)(Ni,Co)5, LaMg2Ni9, (La,Nd)2Ni7 and LaNi3 phases expanded with Co and Al element added. The hydrogen storage capacity initially increased from 1.36 (x=0) to 1.47 wt.% (x=0.3) and then decreased to 1.22 wt.% (x=0.5). The discharge capacity retention and cycle stability of the alloy electrodes were improved with the increase of Co and Al contents. The La0.55Pr0.05Nd0.15Mg0.25Ni3.5(Co0.5Al0.5)0.3 alloy electrode possessed better electrochemical kinetic characteristic.     

Study on structure and electrochemical properties of the （LaGdMg）Ni3.35-xCoxAl0.15（x=0-2.0） hydrogen storage alloys

Hydrogen storage alloys(LaGdMg)Ni3.35-xCoxAl0.15(x=0,0.1,0.3,0.5,1.0,1.5,2.0) were prepared by induction melting followed by annealing treatment in argon atmosphere.The effects of partly replacing Ni by Co element in(LaGdMg)Ni3.35Al0.15 on the phase structure and electrochemical properties of(LaGdMg)Ni3.35-xCoxAl0.15 alloys were investigated.Structure analysis showed that the alloys consisted of Ce2Ni7-type(Gd2Co7-type),CaCu5-type,Pr5Co19-type,PuNi3-type phase structure.The addition of Co element obviously reduced the contents of CaCu5-type phase and increased the contents of Ce2Ni7-type phase.However,Pr5Co19-type and CaCu5-type phase obviously increased with the high content of Co.Rietveld analysis showed that the c-axis lattice parameters and cell volumes of the component phases increased with increasing Co content.The electrochemical measurements showed that as the Co content increased,the maximum discharge capacity and the cyclic stability of the annealed alloys both first increased then decreased.The(LaGdMg)Ni3.05Co0.3Al0.15 alloy electrode exhibited the maximum discharge capacity(392.92 mAh/g),and the(LaGdMg)Ni1.85Co1.0Al0.15 alloy electrode showed the best cyclic stability(S100=96.1%).     

AB5型与AB3.5型贮氢合金的电化学性能对比研究

为了对比研究AB5型与AB3.5型贮氢合金的电化学及动力学特性,以AB5型MlNi3.68Mn0.32Co0.73Al0.27和AB3.5型Ml0.80Mg0.20 （NiMnAlCu）3.6、La0.6 Mg0.4 Ni3.5为研究对象.采用XRD分析了合金的相结构,利用电化学方法测试合金的电化学及动力学特性.结果发现,MlNi3.68 Mn0.32Co0.73Al0.27合金由单相LaNi5相组成,而Ml0.80Mg0.20（NiMnAlCu）3.6、La0.6Mg0.4Ni3.5均有LaNi5相和La2Ni7相组成.AB3.5型合金的放电容量、荷电保持率以及动力学特性高于AB5型合金.     

MMNi_5基贮氢合金的电极特性

测定了ＭＭＮｉ５基贮氢合金的电极特性。用快淬法制成的ＭＭ（０．９）Ｔｉ（０．１）Ｎｉ（３．９）Ｍｎ（０．４）Ｃｏ（０．４）Ａｌ（０．３）贮氢合金电极的循环寿命和快速放电能力显著提高，其３００次充放电循环后电容量仅下降１８％，这与合金中微晶组织的形成有关，而感应熔炼制成的ＭＭ（０．９）Ｔｉ（０．１）Ｎｉ（３．９）Ｍｎ（０．４）Ｃｏ（０．４）Ａｌ（０．３）贮氢合金电极２００次循环后电容量下降３９％，经１０００℃３ｈ退火后，其３００次循环后电容量下降为２７％。     

Electrochemical performance of Gd-Co-Mn alloys

The Gd-Co-Mn alloys with compositions of Gd33.3Co66.7,Gd33.3Mn66.7,Gd22.2Co74.8Mn3 and Gd25Co70Mn5 were prepared and examined by X-ray diffractometer.The electrochemical properties of these alloys such as discharge capacity,cycling performance and high rate dischargeability were investigated by battery testing instruments in alkaline electrolyte.The discharge capacity of Gd22.2Co74.8Mn3 was the highest among these alloys at the same discharge current density,and the maximum value was 376.7 mAh/g discharged at 150 mA/g.The discharge capacities of the alloys Gd33.3Co66.7 and Gd33.3Mn66.7 reached their maxima(about 225 and 325 mAh/g)at discharge current density of 150 mA/g.A comparison of the electrochemical performance of the Gd-Co-Mn alloys revealed that the alloy Gd22.2Co74.8Mn3 possessed better electrochemical performance and had better discharge capacity,cycle stability,while the alloy Gd25Co70Mn5 had a better high rate discharge ability.In general,the electrochemical performance of ternary alloys was better than binary alloys in this case.